Synthesis and characterization of novel Ru(III) complexes of 2‐aminopyrazine: Interaction with biomolecules, antineoplastic activity, and computational investigation

Synthesis and characterization of novel Ru(III) complexes of 2-aminopyrazine: Interaction with biomolecules, antineoplastic activity, and computational investigation

Ruthenium (III) anticancer candidates have been synthesized and characterized experimentally and theoretically. Their binding affinity toward biomacromolecules, in vitro anticancer activity, apoptosis, cell cycle and gene expression, and molecular docking have been explored.


Ruthenium (III) complexes (13) of 2-aminopyrazine (pyz) with general formula of [Hpyz][RuCl4(DMSO)(pyz)](1), Na[RuCl4(pyz)(DMSO)] (2), and (Hpyz)[RuCl4(pyz)2].2H2O (3) have been synthesized and characterized by elemental analyses, FTIR, 1H NMR, and UV–visible spectroscopy, along with the magnetic susceptibility and cyclic voltammetry measurements. The molecular structures of the complexes have also been optimized using density functional theory (DFT) calculation which demonstrates an octahedral geometry to be adopted by the Ru(III) ion. The UV–visible and fluorescence spectra were employed to study the interaction of the compounds with nucleic acid (ctDNA and tRNA) and bovine serum albumin (BSA). The data showed a higher tendency for the ligand and its complexes (13) to interact with biomolecules (1 > 2 > 3). All complexes showed potent in vitro anticancer activity against three human cancer cell lines and high safety against normal cell lines as complex (1) is the most active one, it was selected for the flow cytometric evaluation for cell death mode, cell cycle analysis, and matrix metalloproteinase-9 (MMP9) expression in treated MDA-231 cells. Proliferating cell nuclear antigen (PCNA) expression and VEGF concentration were evaluated in the treated cells and compared with the untreated ones. Our study proved that complex (1) arrests the cell cycle, inhibits DNA transcription, reduces both MMP9 (validated by our molecular docking investigation targeting MMP9 protein) and PCNA expressions, and induces apoptotic cell death, leading to cancer metastasis prevention.

Stimuli‐triggered Self‐Assembly of Gold Nanoparticles: Recent Advances in Fabrication and Biomedical Applications

Stimuli-triggered Self-Assembly of Gold Nanoparticles: Recent Advances in Fabrication and Biomedical Applications

This review summarizes recent progress in the development of stimuli-triggered self-assembly on gold nanoparticles and introduce the breakthrough of gold nanoparticles in disease diagnosis and treatment. In addition, the current challenge and future prospective of stimuli-responsive gold nanoparticles for biomedical applications are discussed.


Abstract

Gold nanoparticles have been widely used in engineering, material chemistry, and biomedical applications owing to their ease of synthesis and functionalization, localized surface plasmon resonance (LSPR), great chemical stability, excellent biocompatibility, tunable optical and electronic property. In recent years, the decoration and modification of gold nanoparticles with small molecules, ligands, surfactants, peptides, DNA/RNA, and proteins have been systematically studied. In this review, we summarize the recent approaches on stimuli-triggered self-assembly of gold nanoparticles and introduce the breakthrough of gold nanoparticles in disease diagnosis and treatment. Finally, we discuss the current challenge and future prospective of stimuli-responsive gold nanoparticles for biomedical applications.

Front Cover: Anisotropic Colloidal Particles by Molecular Self‐Assembly: Synthesis and Application (ChemNanoMat 3/2024)

Front Cover: Anisotropic Colloidal Particles by Molecular Self-Assembly: Synthesis and Application (ChemNanoMat 3/2024)

Anisotropic colloidal particles have attracted great attention over the past few decades because of their significant properties that differ from isotropic particles. Molecular self-assembly provides the possibility to design and construct anisotropic colloidal particles from the single-molecule level, and molecular assemblies can both inherit the properties of molecules in single states and integrate the functions of molecules in collective states, which has attracted great interest to researchers. This review article briefly summarizes the research progress of molecules from small molecules, block copolymers and homopolymers to anisotropic particles, including their self-assembly strategies and applications. Finally, the remaining challenges of this topic and future developments in this field have been discussed. More information can be found in the Review by Bing Liu et al.


FRET‐Amplified Singlet Oxygen Generation by Nanocomposites Comprising Ternary AgInS2/ZnS Quantum Dots and Molecular Photosensitizers

FRET-Amplified Singlet Oxygen Generation by Nanocomposites Comprising Ternary AgInS2/ZnS Quantum Dots and Molecular Photosensitizers

Novel water-soluble nanocomposite based on hydrophobic tetraphenylporphyrin molecules and hydrophilic ternary AgInS2/ZnS quantum dots incorporated into a chitosan matrix was fabricated for applications in antibacterial photodynamic therapy. The enhanced singlet oxygen generation by the formed nanocomposites can be observed due to the efficient resonance energy transfer from ternary quantum dots to tetraphenylporphyrin molecules.


Abstract

Antibacterial photodynamic therapy (a-PDT) has emerged as a promising non-invasive therapeutic modality that utilizes the combination of a photosensitive agent, molecular oxygen, and excitation light to generate reactive oxygen species (ROS), demonstrating remarkable activity against multidrug-resistant bacterial infections. However, the effective use of conventional photosensitizers is significantly limited by a number of their shortcomings, namely, poor water solubility and low selectivity. Herein, we present a novel biocompatible water-soluble nanocomposite based on hydrophobic tetraphenylporphyrin (TPP) molecules and hydrophilic ternary AgInS2/ZnS quantum dots incorporated into a chitosan matrix as an improved photosensitizer for a-PDT. We demonstrated that TPP molecules could be successfully transferred into chitosan solution while remaining primarily in the form of monomers, which are capable of singlet oxygen generation. We performed a detailed analysis of the Förster resonance energy transfer (FRET) between quantum dots and TPP molecules within the nanocomposite and proposed the mechanism of the singlet oxygen efficiency enhancement via FRET.

Anisotropic Colloidal Particles by Molecular Self‐Assembly: Synthesis and Application

Anisotropic Colloidal Particles by Molecular Self-Assembly: Synthesis and Application

Molecular self-assembly becomes an attractive strategy for the preparation of anisotropic colloidal particles that inherit the properties of molecules in single states and the new functions resulting from the coupling between molecules. This article reviews the recent progress towards molecular self-assembly of anisotropic colloids, focusing on molecular self-assembly strategies and their applications.


Abstract

Anisotropic colloidal particles have attracted great attention over the past few decades because of their significant properties that differ from isotropic particles. Molecular self-assembly provides the possibility to design and construct anisotropic colloidal particles from the single-molecule level, and molecular assemblies can both inherit the properties of molecules in single states and integrate the functions of molecules in collective states, which has attracted great interest to researchers. Even in recent years, the self-assembly strategy of anisotropic colloidal particles has been greatly developed. This review article briefly summarizes the research progress of molecules from small molecules, block copolymers and homopolymers to anisotropic particles, including their self-assembly strategies and applications. Finally, we discuss the remaining challenges of this topic and we expect that by manipulating the design of diverse molecules/polymers, anisotropic colloidal particles can evolve into a new era.

Formation of N‐doped Graphene and Carbon Nanoparticles Integrated Composite for Efficient Oxygen Reduction Electrocatalysis

Formation of N-doped Graphene and Carbon Nanoparticles Integrated Composite for Efficient Oxygen Reduction Electrocatalysis

A self-assemble N-doped graphene and N-doped carbon nanoparticles integrated composite has been prepared by a multi-step acid etching plus annealing method. The formation of N-doped graphene is likely based on a “decomposition and recrystallization” mechanism without the use of any metallic catalyst. The as-prepared integrated composite exhibits efficient catalytic activity for four-electron oxygen reduction reaction.


Abstract

N-doped carbon-based materials have been regarded as promising alternatives to Pt-based electrocatalysts for the four-electron (4e) oxygen reduction reaction (ORR), which is an important electrochemical reaction for the polymer electrolyte fuel cells. Here, we report a N-doped graphene and N-doped carbon nanoparticles integrated composite electrocatalyst by a multi-step acid etching plus annealing method. Despite the low N-doping level, the material exhibits efficient 4e ORR activity with an onset potential of 0.932 V, a half-wave potential of 0.814 V, and a limiting current density of 5.3 mA cm−2 in 0.1 M KOH solution. We demonstrate that the promoted 4e ORR activity is attributed to the special 2D–0D integrated structure for exposing massive active sites, the favorable porous structure facilitating the H2O transfer dynamics, and the high content of oxygen-containing C−O−C species and the increased intrinsic carbon defects for additional active sites. A “decomposition and recrystallization” mechanism is proposed for the formation of N-doped graphene.

Gold Microstructures by Thermolysis of Gold(III) Di‐isopropyldithiocarbamate Complexes

Gold Microstructures by Thermolysis of Gold(III) Di-isopropyldithiocarbamate Complexes

The reaction between gold(III) chloride and sodium di-isopropyldithiocarbamate produces two compounds. Sub-micron sized gold microcrystals are produced when the complexes are thermally decomposed in the solid-state. The morphology of the resultant gold microcrystals is determined by the choice of complex.


Abstract

Elemental gold was formed by thermolysis of gold(III) dithiocarbamate single-source precursors, which exist as two complexes. The complexes were readily synthesised from the reaction between chloroauric acid and sodium di-isopropyldithiocarbamate and could be isolated from each other. The thermal decomposition processes were evaluated using thermogravimetry and electrical resistance measurements. The structure and purity of the resultant gold was examined using scanning electron microscopy. The resultant gold materials were drastically different and dependent on the thermolysed complex.

Design and Preparation of a Bifunctional Nanobiohybrid Catalyst by Combining Palladium and α‐Amylase Enzyme: Application in One‐pot Chemoenzymatic Catalysis

Design and Preparation of a Bifunctional Nanobiohybrid Catalyst by Combining Palladium and α-Amylase Enzyme: Application in One-pot Chemoenzymatic Catalysis

A heterogeneous recyclable nanobiohybrid catalyst was developed by combining palladium nanoparticles and α-amylase enzyme. Further, the developed catalyst was employed to catalyze the one-pot chemoenzymatic synthesis of functionalized biphenyls and bis(indolyl)methanes.


Abstract

A chemoenzymatic approach that combines chemical and bio-catalyst has proven very useful in synthetic chemistry, however, mutual deactivation of chemical and bio-catalyst when employed in the same pot is still a challenge. In this context, the development of nanobiohybrid catalysts has played an important role and overcoming the issue of mutual deactivation between catalysts to a certain extent. Herein, we design and synthesize a novel heterogeneous recyclable nanobiohybrid catalyst comprising palladium nanoparticles and α-amylase from Aspergillus oryzae immobilized onto halloysite nanotubes as a solid heterogeneous support. Further, the wider applicability of the developed nanobiohybrid catalyst is revealed in the one-pot chemoenzymatic synthesis of functionalized biphenyls and bis(indolyl)methanes which consists of Pd-catalyzed Suzuki-Miyaura coupling and α-amylase mediated aza-Michael addition or electrophilic substitution reactions respectively. Further, the robustness and generality of the developed one-pot chemoenzymatic synthesis are demonstrated by incorporating different substitutions at the starting materials and obtaining the corresponding products in moderate to good yields.

In‐Situ Colloidal Synthetic Route to Monodispersed NiCo2S4 Nanoparticles over Nickel Foam for High‐Performance Supercapacitive Charge Storage

In-Situ Colloidal Synthetic Route to Monodispersed NiCo2S4 Nanoparticles over Nickel Foam for High-Performance Supercapacitive Charge Storage

Monodispersed NiCo2S4 nanoparticles are grown in-situ on nickel foam by a one-step colloidal synthetic route, and they deliver a high specific capacitance of 1790.8 F/g at 1 A/g via a three-electrode system and also maintain outstanding energy-storage capacity, high energy density and stability in a two-electrode cell. This study provides a feasible way to design and fabricate electrodes effectively.


Abstract

One-step colloidal synthetic route was adopted to in-situ grow monodispersed NiCo2S4 nanoparticles (NPs) on nickel foam (NF) from metallic salts with benzyl disulfide in the media of oleylamine and octadecene. Owing to the favorable dispersion and considerable redox activity of NiCo2S4 along with tight and binder-free connection with NF, the obtained battery-type supercapacitor delivered a specific capacitance of 1790.8 F g−1 at 1 A g−1 via a three-electrode system. Simultaneously, it just degraded 40 % at 20 A g−1 and maintained 86.8 % of initial specific capacitance (C0) after 2000 cyclic trials at 10 A g−1. When the NiCo2S4 NPs were assembled with active carbon (AC) forming an asymmetric capacitor device of NiCo2S4 NPs//AC, it delivered an energy density (E) of 48.7 W h kg−1 at a power density (P) of 161.1 W kg−1, and kept 21.9 W h kg−1 at a high P of 8.05 kW kg−1. Meanwhile, the capacitor manifested preeminent cycling life (C=94.5 % C0 after 5000 cyclic trials) at 5 A g−1. The in-situ grown NiCo2S4 NPs on NF without any binder exhibited high performance in energy storage, providing a feasible way to improve the electrochemical performance of the electrode materials.

Directional Growth of Bi2WO6 with Highly Exposed Facets on 2D‐Co3O4 for different Properties under two Light Sources

Directional Growth of Bi2WO6 with Highly Exposed Facets on 2D-Co3O4 for different Properties under two Light Sources

We synthesized a novel p-n heterojunction with rose-like morphology self-assembled from 2D-Co3O4 and Bi2WO6 nanosheets with highly exposed {010} facets, named Bi2WO6/Co3O4 composite. It was considered that the composite served as a traditional heterojunction under ultraviolet light, while it played a role as a Z-scheme photocatalyst under visible light, respectively.


Abstract

A composite of two or more materials usually results in enhanced specific properties. In this paper, a kind of composite material composed of Bi2WO6 with highly exposed {010} facets and 2D-Co3O4 was prepared by a one-pot reaction and then applied to decontaminate hydrocortisone in wastewater. The Bi2WO6/Co3O4 composite possessed a rose-like surface microtopography self-assembled from Bi2WO6 and Co3O4 nanosheets. The micro-interface analysis showed that {110} facets of Co3O4 and {010} facets of Bi2WO6 were glued in situ and formed heterojunction. Additionally, the removal ability of hydrocortisone through Bi2WO6/Co3O4 varied under different light sources, which was 85.0 % under ultraviolet light and 97.3 % under visible light within 60 min. It was considered that Bi2WO6/Co3O4 was similar to a traditional heterojunction and the major reactive species was H2O2 under ultraviolet light, while it played a role as a Z-scheme photocatalyst and the major reactive species was ⋅OH under visible light. Finally, product analysis of hydrocortisone demonstrated that the dexter chain broke whatever under ultraviolet or visible light, but the breakage of parent nucleus appeared only under visible light. This research revealed the enhanced catalytic properties of p-n heterojunction catalysts and indicated the specifically exposed facets are promising for organic contaminants in water.